Synthesis and Characterization of Ethylenedithio-MPTTF-PTM Radical Dyad as a Potential Neutral Radical Conductor

Souto, Manuel; Jensen, Michael Hansen; Diez‐Cabanes, Valentin; Cornil, Jérôme; Jeppesen, Jan O.; Ratera, Imma; Rovira, Concepció; Veciana, Jaume

doi:10.3390/magnetochemistry2040046

Cited by 4 publications

(4 citation statements)

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“…Therefore, the coupling and column chromatography steps were carried out at the alcohol stage. Earlier reports aiming at building conjugated systems with perchlorinated trityl radicals (PTM-radicals) used Horner–Wadsworth–Emmons reactions, , which are less versatile then the Suzuki–Miyaura reaction employed here.…”

Section: Resultsmentioning

confidence: 99%

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C–C Cross-Coupling Reactions of Trityl Radicals: Spin Density Delocalization, Exchange Coupling, and a Spin Label

et al. 2019

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Organic radicals are usually highly reactive and short-lived species. In contrast, tetrathiatriarylmethyl radicals, the so-called trityl- or TAM-radicals, are stable and do survive over longer times even under in-cell conditions. In addition, they show strong EPR signals, have long phase memory times at room temperature, and are reporters on local oxygen and proton concentrations. These properties facilitated their use for magnetic resonance imaging, dynamic nuclear polarization, and spin-labeling EPR under in-cell conditions. Thus, synthetic approaches are required for functionalization of TAM radicals tailored to the desired application. However, most TAM derivatives reported in the literature are based on esterification of the Finland trityl, which is prone to hydrolysis. Here, we report on an approach in which TAM is site-selective iodinated and subsequently C–C cross-coupled to various building blocks in a modular approach. This yields conjugated trityl compounds such as a trityl attached to a porphyrin, an alkinyl functionalized trityl radical, and a strongly exchange-coupled trityl biradical. This synthesis approach thus has implications not only for magnetic resonance spectroscopy but also for the design of molecular magnets or quantum computing devices.

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Section: Resultsmentioning

confidence: 99%

“…Earlier reports aiming at building conjugated systems with perchlorinated trityl radicals (PTM-radicals) used Horner− Wadsworth−Emmons reactions, 60,61 which are less versatile then the Suzuki−Miyaura reaction employed here. Sonogashira−Hagihara Coupling.…”

Section: ■ Introductionmentioning

confidence: 99%

C–C Cross-Coupling Reactions of Trityl Radicals: Spin Density Delocalization, Exchange Coupling, and a Spin Label

et al. 2019

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“…Absorption spectra of radical dyad 1 were measured in different solvents in order to compare it with the solvatochromic behavior observed in related TTF‐PTM radical dyads . This solvatochromism is assigned to the bistability phenomenon between neutral and zwitterionic species since polar solvents can induce an intramolecular electron transfer process from the electron‐donor TTF unit to the electron‐acceptor PTM radical.…”

Section: Methodsmentioning

confidence: 99%

Role of the Open‐Shell Character on the Pressure‐Induced Conductivity of an Organic Donor–Acceptor Radical Dyad

Souto

Gullo

Cui

et al. 2018

Chemistry A European J

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Single-component conductors based on neutral organic radicals have received a lot of attention due to the possibility that the unpaired electron can serve as a charge carrier without the need of a previous doping process. Although most of these systems are based on delocalized planar radicals, we present here a nonplanar and spin localized radical based on a tetrathiafulvalene (TTF) moiety, linked to a perchlorotriphenylmethyl (PTM) radical by a conjugated bridge, which exhibits a semiconducting behavior upon application of high pressure. The synthesis, electronic properties, and crystal structure of this neutral radical TTF-Ph-PTM derivative (1) are reported and implications of its crystalline structure on its electrical properties are discussed. On the other hand, the non-radical derivative (2), which is isostructural with the radical 1, shows an insulating behavior at all measured pressures. The different electronic structures of these two isostructural systems have a direct influence on the conducting properties, as demonstrated by band structure DFT calculations.

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“…Molecular radical units with unpaired electrons have been the basis of one of the earliest devised strategies for achieving organic conductors. In the contribution of Manuel Souto et al [6], a new molecular dyad is reported, based on a monopyrrolo-tetrathiafulvalene electron donor linked by a π-conjugated bridge to a perchlorotriphenylmethyl radical, with interesting properties and the potential to give rise to new radical conductors in the solid state. The combination of radical units with electroactive donor networks is another strategy for preparing magnetic conductors, and in this issue Kazuki Horikiri and Hideki Fujiwara describe charge transfer salts of a new EDT-TTF (ethylenedithiotetrathiafulvalene) donor containing a radical through a π-conjugated vinylene spacer, with diamagnetic GaCl 4 and paramagnetic FeCl 4 anions with strong π-d interactions [7].…”

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confidence: 99%

Magnetism of Molecular Conductors

Almeida

2017

Magnetochemistry

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The study of the magnetic properties of molecular conductors has experienced, during the last decades, a very significant evolution, comprising systems of increasing molecular complexity and moving towards multifunctional materials, namely by their incorporation in conducting networks of different paramagnetic centers. In this context, molecular magnetic conductors have emerged at the intersection between the fields of molecule-based conductors and molecule-based magnets as a very exciting class of multifunctional materials in which the interaction and synergy between conduction electrons and localized magnetic moments can lead to new phenomena, complex phase diagrams, and different ground states, with a large potential for technological applications, namely in electronic devices, sensors and in spintronics. Among these phenomena are unusual field-induced transitions, including magnetic field-induced superconductivity, very large magnetoresistance effects, conductors that are switchable by magnetic field, changes of magnetic ordering or spin state, etc.This Special Issue of Magnetochemistry features a collection of research contributions illustrating recent achievements in different aspects of this topic concerning the development, study and understanding of the magnetic properties of molecular conductors and their applications. Quite different types of compounds are considered.A contribution by Tamotsu Inabe et al.[1], reviews a series of compounds based on axially ligated phthalocyanines. Metal phthalocyanines are one of the first examples of compounds where, in addition to delocalized π-conduction electrons in the ligand, there can also be localized magnetic moments for some metals. The π-d interaction of these local moments embedded in the sea of conduction electrons has long since been identified as a source of possible interesting phenomena. In this contribution, the properties of TPP[M(Pc)(CN) 2 ] 2 compounds (TPP = tetraphenylphosphonium, Pc = phthalocyaninato), with M = Fe and Cr are reviewed, emphasizing carrier localization and charge disproportionation enhanced by the interaction between local magnetic moments and conduction π-electrons (π-d interaction), and the large negative magnetoresistance, reflecting the difference in the anisotropy of different d-d, π-d, and π-π interactions.Two other contributions in this issue concern a family of compounds with two types of chains (conducting and magnetic), based on the organic perylene donor and inorganic [M(mnt) 2 ] anions, which have been studied for more than 30 years, but are still unique among molecular materials. In a review by Jean-Paul Pouget et al. [2], the structural instabilities exhibited of these salts are reviewed and discussed in relation to the magnetic properties of the 1D spin-Peierls (SP) instability of the dithiolate stacks, showing, in particular, that α-(Per) 2 [M(mnt) 2 ] salts exhibit the physical properties expected of a two-chain Kondo lattice. In another contribution by Manuel Matos et al. [3], these compounds are also addressed, ...

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Synthesis and Characterization of Ethylenedithio-MPTTF-PTM Radical Dyad as a Potential Neutral Radical Conductor

Cited by 4 publications

References 24 publications

C–C Cross-Coupling Reactions of Trityl Radicals: Spin Density Delocalization, Exchange Coupling, and a Spin Label

C–C Cross-Coupling Reactions of Trityl Radicals: Spin Density Delocalization, Exchange Coupling, and a Spin Label

Role of the Open‐Shell Character on the Pressure‐Induced Conductivity of an Organic Donor–Acceptor Radical Dyad

Magnetism of Molecular Conductors

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